Oral care compositions and methods

ABSTRACT

Provided is an oral care composition comprising a phosphate/acrylate co-polymer, a synthetic anionic linear polycarboxylate polymer, and an orally acceptable carrier; and methods of using the same.

BACKGROUND

Many individuals desire a “bright” smile and white teeth, and considerdull and stained teeth cosmetically unattractive. Unfortunately, withoutpreventive or remedial measures, stained teeth are almost inevitable dueto the absorbent nature of dental material. Everyday activities such assmoking or other oral use of tobacco products, and eating, chewing ordrinking certain foods and beverages (in particular coffee, tea coke,and red wine), cause undesirable staining of surfaces of teeth. Stainingcan also result from microbial activity, including that associated withdental plaque. The chromogens or color causing substances in thesematerials become part of the pellicle layer and can permeate the enamellayer. Even with regular brushing and flossing, years of chromogenaccumulation can impart noticeable tooth discoloration.

A tooth is comprised of an inner dentin layer and an outer hard enamellayer that is the protective layer of the tooth. The enamel layer of atooth is naturally opaque, and white or a slightly off-white color. Theenamel layer is composed of hydroxyapatite mineral crystals that createa somewhat porous surface. These hydroxyapatite crystals formmicroscopic hexagonal rods or prisms that make up the enamel surface. Asa result, the surface of the enamel presents microscopic spaces or poresbetween the prisms. Without limiting the mechanism, function, or utilityof the present disclosure, it is believed that this porous nature of theenamel is where discoloring substances permeate the enamel and discolorthe teeth.

To combat staining and brighten or restore the natural enamel color,products containing bleaching materials are commercially available forprofessional and consumer use. The most commonly accepted chemicals usedin teeth whitening today are peroxides. Peroxides are generally deemedsafe from a physiological standpoint, and can be effective to whitenteeth. Such peroxides include hydrogen peroxide, carbamide peroxide,sodium perborate, and sodium percarbonate. When these peroxides are inappropriate contact with teeth they will usually oxidize stains,rendering the teeth whiter.

Professional dental treatments frequently include a tooth surfacepreparation such as acid etching followed by the application of highlyconcentrated bleaching solutions (e.g. up to 37% hydrogen peroxide)and/or the application of heat or light. (See, e.g., U.S. Pat. Nos.5,425,953 and 5,766,574.) These procedures provide rapid results, butare expensive, and often require several trips to the dentist. In manycases, the patient's lips are uncomfortably retracted during the entiretreatment and the patient is confined to sitting in the dental chair.

Alternatively, at home bleaching systems can be used. These systems havegained significant popularity in the past decade because of reducedcost, and increased convenience.

Current home treatment methods include abrasive toothpastes, toothpastesthat produce oxides, whitening gels for use with a dental tray andwhitening strips. The effectiveness of such techniques depends on avariety of factors including the type and intensity of the stain, thetype of bleaching agent, contact time of the bleaching agent on theteeth, the amount of available bleaching active in the composition theability of the bleaching agent to penetrate the tooth enamel, andconsumer compliance. Effectiveness is also dependent on the amount ofbleaching active in the composition, the ability of the active to bereleased during use, and the stability of the active in the product.However, the effectiveness of many of these treatments is adverselyaffected because of deficiencies in one or more factors relating to thecomposition and consumer compliance.

Biofilms form when bacteria adhere to surfaces in some form of wateryenvironment and begin to excrete a slimy, glue-like substance that canstick to all kinds of materials—metals, plastics, soil particles,medical implant materials, biological tissues. Biofilms can be formed bya single bacterial species, but biofilms more often consist of manyspecies of bacteria, as well as fungi, algae, protozoa, debris, andcorrosion products. Essentially, a biofilm may form on any surfaceexposed to bacteria and some amount of water. Dental plaque is ayellowish biofilm that builds up on the teeth. Biofilms containcommunities of disease-causing bacteria and their uncontrolledaccumulation has been associated with cavities and gum disease (bothgingivitis and periodontitis).

There is thus a need for novel oral compositions and methods that mayinhibit staining and/or biofilm formation.

BRIEF SUMMARY

Provided herein is an oral care composition comprising aphosphate/acrylate co-polymer, a synthetic anionic linearpolycarboxylate, and an orally acceptable carrier.

Also provided is a method of forming the composition as a mouth rinsethat includes the phosphate/acrylate co-polymer and the syntheticanionic linear polycarboxylate polymer as well as a zinc salt and acationic antibacterial agent comprising:

-   (I) mixing water, surfactant, and a cationic antibacterial agent in    a mixing tank to form a main mix;-   (II) mixing 10-20 weight % of the total water, optionally 14-16 or    15 weight % of the total water, the phosphate/acrylate co-polymer,    and a polyol (such as glycerin and/or sorbitol) to form a first    premix,-   (III) mixing 10-20 weight % of the total water, optionally 14-16 or    15 weight % of the total water first with the zinc salt (such as    water soluble zinc salt, such as zinc chloride) and then adding the    synthetic anionic linear polycarboxylate polymer (Gantrez) to form a    second premix,-   (IV) mixing the first premix into the main mix,-   (V) after the first premix is added, mixing the second premix into    the main mix,-   (VI) optionally, mixing flavor and/or cooling agents with a glycol    to form a third premix and adding the third premix to the main mix    after the second premix is added.

Further areas of applicability of the present invention will becomeapparent from the detailed description provided hereinafter. It shouldbe understood that the detailed description and specific examples, whileindicating the preferred embodiment of the invention, are intended forpurposes of illustration only and are not intended to limit the scope ofthe invention.

DETAILED DESCRIPTION

The following description of the preferred embodiment(s) is merelyexemplary in nature and is in no way intended to limit the invention,its application, or uses.

As used throughout, ranges are used as shorthand for describing each andevery value that is within the range. Any value within the range can beselected as the terminus of the range. In addition, all references citedherein are hereby incorporated by referenced in their entireties. In theevent of a conflict in a definition in the present disclosure and thatof a cited reference, the present disclosure controls.

Unless otherwise specified, all percentages and amounts expressed hereinand elsewhere in the specification should be understood to refer topercentages by weight. The amounts given are based on the active weightof the material.

As used herein, an “oral care composition” refers to a composition forwhich the intended use can include oral care, oral hygiene, or oralappearance, or for which the intended method of use can compriseadministration to the oral cavity. In some embodiments, an oral carecomposition is not intentionally swallowed, but is rather retained inthe oral cavity for a time sufficient to effect the intended utility.The oral care compositions as disclosed herein may be used in nonhumanmammals such as companion animals (e.g., dogs and cats), as well as byhumans. In some embodiments, the oral care compositions as disclosedherein are used by humans.

As used herein, “phosphate/acrylate co-polymer” refers to a polymer madeup of acrylate monomers and phosphate-bearing monomers, e.g., aco-polymerized product of a mixture of acrylic acid, methacrylic acid,and 2-hydroxyethyl methacrylate phosphates of Formula 1:

wherein n is 0, 1 or 2. In some embodiments, the phosphate/acrylateco-polymer is a co-polymerized product of a mixture of acrylic acid,methacrylic acid, and 2-hydroxyethyl methacrylate phosphates of Formula1, comprising acrylic acid in a molar percentage of 70-90%, 80-90%, orabout 85%; methacrylic acid in a molar percentage of 5-20%, 5-15%, orabout 11%, and hydroxyethyl methacrylate phosphates of Formula 1 in amolar percentage of 1-10%, 2-6%, or about 4%. In some embodiments, thephosphate/acrylate co-polymer has a weight average molecular weight offrom 10 to 500 kDa, optionally, 10 to 200 kDa, 10 to 40 kDa, 15 to 25,or 17 to 23 kDa, and the phosphate/acrylate co-polymer is below itsglass transition temperature. In certain embodiments, the weight averagemolecular weight is 10 to 40 kDa. In other embodiments, the weightaverage molecular weight is 17 to 23 kDa. For example, in a particularembodiment, the phosphate/acrylate copolymer is a random copolymer thatis the copolymerized product of a mixture of, in the relative amountsset forth in Table 1 below, 2-hydroxyethy methacrylate phosphates,acrylic acid, and methacrylic acid.

TABLE 1 Mono- Mono- mer mer Weight Molar Ratio Ratio (weight (MoleMonomer Name and Structure %) %)

11 4

75 85

14 11

Phosphate/acrylate co-polymers as described include DV8801 (Rhodia).

As used herein, “synthetic anionic linear polycarboxylate” refers to apolymer synthesized by using an olefinically or ethylenicallyunsaturated carboxylic acid that contains an activated carbon-to-carbonolefinic double bond and at least one carboxyl group. The acid containsan olefinic double bond which readily functions in polymerizationbecause of its presence in the monomer molecule either in the alpha-betaposition with respect to a carboxyl group or as part of a terminalmethylene grouping. Illustrative of such acids are acrylic, methacrylic,ethacrylic, alpha-chloroacrylic, crotonic, beta-acryloxy propionic,sorbic, alpha-chlorsorbic, cinnamic, beta-styrilacrylic, muconic,itaconic, citraconic, mesaconic, glutaconic, aconitic,alpha-phenylacrylic, 2-benzyl acrylic, 2-cyclohexylacrylic, angelic,umbellic, fumaric, maleic acids and anhydrides. Other olefinic monomerscopolymerizable with such carboxylic monomers include vinyl acetate,vinyl chloride, dimethyl maleate and the like. The synthetic anioniclinear polycarboxylate is mainly a hydrocarbon with optional halogen andO-containing substituents and linkages as present in for example ester,ether, and OH groups. The carboxyls may be in the form of the acid(—COOH) or carboxylate anion (—COO⁻). The copolymers preferably containsufficient carboxyl groups for water-solubility and adherence to plaque.The terms “synthetic” and “linear” do not include known thickening orgelling agents comprising carboxymethylcellulose and other derivativesof cellulose and natural gums, nor Carbopols having reduced solubilitydue to cross-linkages.

In some embodiments. “synthetic anionic linear polycarboxylate” refersto 1:4 to 4:1 copolymers of maleic anhydride or acid with anotherpolymerizable ethylenically unsaturated monomer. e.g., methyl vinylether (methoxyethylene), having a molecular weight (M.W.) of about30,000 to about 2,500,000; for example 1:4 to 4:1, e.g. about 1:1,copolymers of methyl vinyl ether/maleic anhydride, e.g., in a ratio ofabout 1:1 substantially in an alternating sequence, wherein theanhydride is hydrolyzed following co-polymerization to provide thecorresponding acid, having a molecular weight (M.W.) of about 30,000 toabout 1,000,000, e.g. about 300,000 to about 800,000, e.g., as soldunder the trade name GANTREZ®, e.g., GANTREZ. S-97 Pharmaceutical Grade(M.W. ca. 700,000), available from Ashland Specialty Chemicals, BoundBrook, N.J. 08805.

As used herein. “orally acceptable carrier” refers to any vehicle usefulin formulating the oral care compositions disclosed herein. The orallyacceptable carrier is not harmful to a mammal in amounts disclosedherein when retained in the mouth, without swallowing, for a periodsufficient to permit effective contact with a dental surface as requiredherein. In general, the orally acceptable carrier is not harmful even ifunintentionally swallowed. Suitable orally acceptable carriers include,for example, one or more of the following: water, a thickener, a buffer,a humectant, a surfactant, an abrasive, a sweetener, a flavorant, avisual aid (e.g., a pigment, a dye, or a mixture thereof), ananti-caries agent, an anti-bacterial, a whitening agent, a desensitizingagent, a vitamin, a preservative, an enzyme, and mixtures thereof.

As used herein, a “tartar control agent” refers to a compound or amixture of compounds that inhibit the formation of tartar, a mixture ofcalcium phosphates on organic matrices, and/or the deposition of plaqueon teeth to form tartar (calculus).

As used herein, “chemical stain” refers to a discoloration of a dentalsurface caused by adsorption or absorption of a colored agent on or intothe surface, or caused by chemical reaction of material of the dentalsurface (e.g., dental enamel) with a colored or noncolored agentcontacting the surface. “Chemical staining” herein means formationand/or development of a chemical stain.

As used herein, “dental surface” refers to a surface of a natural toothor a hard surface of artificial dentition including a denture, dentalplate, crown, cap, filling, bridge, dental implant and the like. In someembodiments, the dental surface is a natural tooth.

Biofilm comprises a diverse microbial community on the tooth surfaceembedded in a matrix of polymers of bacterial and salivary origin. Oncea tooth surface is cleaned, a conditioning film of proteins andglycoproteins may be adsorbed rapidly to the tooth surface. Biofilmformation involves the interaction between early bacterial colonisersand this film. Subsequently, secondary colonisers adhere to the alreadyattached early colonisers (co-aggregation) and this process contributesto the development of a matured biofilm. Inhibiting the growth ofbiofilm may involve preventing and minimizing the re-attachment ofbacteria onto the tooth surfaces.

The phosphate side group of a phosphate/acrylate co-polymer, asdisclosed herein, may function as an anchor to deposit the co-polymeronto the tooth surface thereby forming a physical layer on the toothsurface that may inhibit staining and/or biofilm formation. Withoutbeing bound by theory, the co-polymer may act by forming a barrier onthe tooth surface ultimately lowering the surface energy for bacterialattachment. The co-polymer may also prevent bacteria from stickingtogether.

Provided herein is an oral care composition (Composition 1) comprising aphosphate/acrylate co-polymer, a synthetic anionic linearpolycarboxylate polymer, and an orally acceptable carrier.

Further provided herein is Composition 1 as follows:

-   -   1.1 Composition 1 wherein the composition comprises 0.1 to 10        weight % phosphate/acrylate co-polymer, e.g., 0.2 to 9 weight %        phosphate/acrylate co-polymer, e.g., 0.3 to 8 weight %        phosphate/acrylate co-polymer, e.g., 0.4 to 7 weight %        phosphate/acrylate co-polymer, e.g., 0.5 to 6 phosphate/acrylate        co-polymer, e.g., e.g., 0.5 to 5 weight % phosphate/acrylate        co-polymer, e.g., 0.5 to 4 weight % phosphate/acrylate        co-polymer, e.g., 0.5 to 3 weight % phosphate/acrylate        co-polymer, e.g., 0.5 to 2 weight % phosphate/acrylate        co-polymer, e.g., 1 to 10 weight % phosphate/acrylate        co-polymer, e.g., 1 to 8 weight % phosphate/acrylate co-polymer,        e.g., 1 to 6 weight % phosphate/acrylate co-polymer, e.g., 1 to        5 weight % phosphate/acrylate co-polymer, e.g., 1 to 4 weight %        phosphate/acrylate co-polymer, e.g., 1 to 3 weight %        phosphate/acrylate co-polymer, e.g., 1 to 2 weight %        phosphate/acrylate co-polymer.    -   1.2 Composition 1 or 1.1 wherein the composition comprises 0.01        to 30 weight % synthetic anionic linear polycarboxylate, e.g.,        0.1 to 30 weight % synthetic anionic linear polycarboxylate,        e.g., 1 to 30 weight % synthetic anionic linear polycarboxylate,        e.g., 5 to 30 weight % synthetic anionic linear polycarboxylate,        e.g., 10 to 30 weight % synthetic anionic linear        polycarboxylate, e.g., 10 to 20 weight % synthetic anionic        linear polycarboxylate. e.g., 15 weight % synthetic anionic        linear polycarboxylate, e.g., 17 weight % synthetic anionic        linear polycarboxylate.    -   1.3 Composition 1, 1.1, or 1.2, wherein the synthetic anionic        linear polycarboxylate is a copolymer of maleic anhydride and        methyl vinyl ether.    -   1.4 Composition 1 or 1.1-1.3 wherein the synthetic anionic        linear polycarboxylate is a 1:4 to 4:1 copolymer of methyl vinyl        ether/maleic anhydride (optionally fully or partially hydrolyzed        following co-polymerization to provide the corresponding acid).    -   1.5 Composition 1 or 1.1-1.4 wherein the synthetic anionic        linear polycarboxylate has a molecular weight (M.W.) of about        30,000 to about 1,000,000. e.g. about 300,000 to about 800,000.    -   1.6 Composition 1 or 1.1-1.5 wherein the composition further        comprises a tartar control agent.    -   1.7 Composition 1.6 wherein the composition comprises 0.1 to 20        weight % tartar control agent, e.g., 0.1 to 15 weight % tartar        control agent, e.g., 0.5 to 15 weight % tartar control agent,        e.g., 15 to 10 weight % tartar control agent, e.g., 1 to 9        weight % tartar control agent, e.g., 1 to 8 weight % tartar        control agent, e.g., 1 to 5 weight % tartar control agent.    -   1.8 Composition 1.6 or 1.7 wherein the tartar control agent        comprises at least one salt comprising phosphorus.    -   1.9 Composition 1.6-1.8 wherein the tartar control agent        comprises at least one of a pyrophosphate salt, a polyphosphate        salt, and a cyclic phosphate salt.    -   1.10 Composition 1.6-1.9 wherein the tartar control agent        comprises at least one of a pyrophosphate salt and a        polyphosphate salt.    -   1.11 Composition 1.6-1.10 wherein the tartar control agent        comprises at least one pyrophosphate salt.    -   1.12 Composition 1.6-1.11 wherein the tartar control agent        comprises 0.1 to 10 weight % of at least one pyrophosphate salt,        e.g., 0.5 to 10 weight % of at least one pyrophosphate salt, 0.5        to 6 weight % of at least one pyrophosphate salt, e.g., 0.5 to 5        weight % of at least one pyrophosphate salt, e.g., 0.5 to 4        weight % of at least one pyrophosphate salt, e.g., 0.5 to 3        weight % of at least one pyrophosphate salt, e.g., 1 to 5 weight        % of at least one pyrophosphate salt, e.g., 1 to 4 weight % of        at least one pyrophosphate salt, e.g., 1 to 3 weight % of at        least one pyrophosphate salt, e.g., 1 to 2 weight % of at least        one pyrophosphate salt.    -   1.13 Composition 1.6-1.12 wherein the tartar control agent        comprises at least one of a di-alkali metal pyrophosphate salt        and a tetra-alkali metal pyrophosphate salt.    -   1.14 Composition 1.6-1.13 wherein the tartar control agent        comprises at least one di-alkali metal pyrophosphate salt.    -   1.15 Composition 1.6-1.14 wherein the tartar control agent        comprises at least one tetra-alkali metal pyrophosphate salt.    -   1.16 Composition 1.6-1.15 wherein the tartar control agent        comprises 0.1 to 10 weight % of at least one tetra-alkali metal        pyrophosphate salt, e.g., 0.1 to 8 weight % of at least one        tetra-alkali metal pyrophosphate salt, e.g., e.g., 0.5 to 6        weight % of at least one tetra-alkali metal pyrophosphate salt,        e.g., 0.5 to 5 weight % of at least one tetra-alkali metal        pyrophosphate salt, e.g., 0.5 to 4 weight % of at least one        tetra-alkali metal pyrophosphate salt, e.g., 0.5 to 3 weight %        of at least one tetra-alkali metal pyrophosphate salt, e.g., 0.5        to 3 weight % of at least one tetra-alkali metal pyrophosphate        salt, e.g., 1 to 5 weight % of at least one tetra-alkali metal        pyrophosphate salt, e.g., 1 to 4 weight % of at least one        tetra-alkali metal pyrophosphate salt, e.g., 1 to 3 weight % of        at least one tetra-alkali metal pyrophosphate salt, e.g., 1 to 2        weight % of at least one tetra-alkali metal pyrophosphate salt.    -   1.17 Composition 1.6-1.16 wherein the tartar control agent        comprises at least one of sodium pyrophosphate (TSPP, Na₄P₂O₇),        potassium pyrophosphate (K₄P₂O₇), disodium dipotassium        pyrophosphate (Na₂K₂P₂O₇), disodium dihydrogen pyrophosphate        Na₂H₂P₂O₇, and dipotassium dihydrogen pyrophosphate K₂H₂P₂O₇.    -   1.18 Composition 1.6-1.17 wherein the tartar control agent        comprises at least one of sodium pyrophosphate (TSPP, Na₄P₂O₇)        and potassium pyrophosphate (K₄P₂O₇).    -   1.19 Composition 1.6-1.18 wherein the tartar control agent        comprises sodium pyrophosphate (TSPP, Na₄P₂O₇).    -   1.20 Composition 1.6-1.19 wherein the tartar control agent        comprises 0.1 to 10 weight % sodium pyrophosphate, e.g., 0.1 to        8 weight % sodium pyrophosphate, e.g., e.g., 0.5 to 6 weight %        sodium pyrophosphate, e.g., 0.5 to 5 weight % sodium        pyrophosphate, e.g., 0.5 to 4 weight % sodium pyrophosphate,        e.g., 0.5 to 3 weight % sodium pyrophosphate, e.g., 0.5 to 3        weight % sodium pyrophosphate, e.g., 1 to 5 weight % sodium        pyrophosphate, e.g., 1 to 4 weight % sodium pyrophosphate, e.g.,        1 to 3 weight % sodium pyrophosphate, e.g., 1 to 2 weight %        sodium pyrophosphate.    -   1.21 Composition 1.6-1.20 wherein the tartar control agent        comprises at least one polyphosphate salt.    -   1.22 Composition 1.6-1.21 wherein the tartar control agent        comprises at least one tripolyphosphate salt.    -   1.23 Composition 1.6-1.22 wherein the tartar control agent        comprises 0.1 to 20 weight % of at least one tripolyphosphate        salt, e.g., 0.5 to 15 weight % of at least one tripolyphosphate        salt, e.g., 1 to 15 weight % of at least one tripolyphosphate        salt, e.g., 1 to 10 weight % of at least one tripolyphosphate        salt, e.g., 2 to 15 weight % of at least one tripolyphosphate        salt, e.g., 2 to 11 weight % of at least one tripolyphosphate        salt, e.g., 2 to 10 weight % of at least one tripolyphosphate        salt, e.g., 2 to 9 weight % of at least one tripolyphosphate        salt, e.g., 2 to 8 weight % of at least one tripolyphosphate        salt, e.g., 2 to 7 weight % of at least one tripolyphosphate        salt, e.g., 3 to 15 weight % of at least tripolyphosphate salt,        e.g., 3 to 10 weight % of at least one tripolyphosphate salt,        e.g., 3 to 9 weight % of at least one tripolyphosphate salt,        e.g., 3 to 8 weight % of at least one tetra-tripolyphosphate        salt, e.g., 3 to 7 weight % of at least one tripolyphosphate        salt.    -   1.24 Composition 1.6-1.23 wherein the tartar control agent        comprises sodium tripolyphosphate (Na₅P₃O₁₀, STPP).    -   1.25 Composition 1.6-1.24 wherein the tartar control agent        comprises 0.1 to 20 weight % sodium tripolyphosphate, e.g., 0.5        to 15 weight % sodium tripolyphosphate, e.g., 1 to 15 weight %        sodium tripolyphosphate, e.g., 1 to 10 weight % sodium        tripolyphosphate, e.g., 2 to 15 weight % sodium        tripolyphosphate, e.g., 2 to 11 sodium tripolyphosphate, e.g., 2        to 10 weight % sodium tripolyphosphate, e.g., 2 to 9 weight %        sodium tripolyphosphate, e.g., 2 to 8 weight % sodium        tripolyphosphate, e.g., 2 to 7 weight % sodium tripolyphosphate,        e.g., 3 to 15 weight % sodium tripolyphosphate, e.g., 3 to 10        weight % sodium tripolyphosphate, e.g., 3 to 9 weight % sodium        tripolyphosphate, e.g., 3 to 8 weight % sodium tripolyphosphate,        e.g., 3 to 7 weight % sodium tripolyphosphate.    -   1.26 Composition 1.6-1.25 wherein the tartar control agent        comprises at least one of sodium hexametaphosphate ((NaPO₃)₆,        SHMP), sodium trimetaphosphate (Na₃P₃O₉, STMP), and a β-phase        calcium pyrophosphate, such as disclosed in U.S. Pat. No.        6,241,974.    -   1.27 Composition 1 or 1.1-1.26 wherein the composition comprises        water, a thickener, a buffer, a humectant, a surfactant, an        abrasive, a sweetener, a flavorant, a visual aid (e.g, a        pigment, a dye, or a mixture thereof), an anti-caries agent, an        anti-bacterial, a whitening agent, a desensitizing agent, a        preservative, or a mixture thereof.    -   1.28 Composition 1 or 1.1-1.27 wherein the composition comprises        water.    -   1.29 Composition 1 or 1.1-1.28 wherein the composition comprises        a thickener.    -   1.30 Composition 1.29 wherein the thickener is a mixture of        thickening silica, carrageenan gum, and sodium        carboxymethylcellulose.    -   1.31 Composition 1 or 1.1-30 wherein the composition comprises a        buffer.    -   1.32 Composition 1.31 wherein the buffer is sodium hydroxide.    -   1.33 Composition 1 or 1.1-1.32 wherein the composition comprises        a humectant.    -   1.34 Composition 1.33 wherein the humectant is a mixture of        glycerin, sorbitol, and propylene glycol.    -   1.35 Composition 1 or 1.1-1.34 wherein the composition comprises        a surfactant.    -   1.36 Composition 1.35 wherein the surfactant is sodium lauryl        sulfate.    -   1.37 Composition 1 or 1.1-1.36 wherein the composition comprises        an abrasive.    -   1.38 Composition 1.37 wherein the abrasive comprises silica.    -   1.39 Composition 1 or 1.1-1.38 wherein the composition comprises        a sweetener.    -   1.40 Composition 1.39 wherein the sweetener is sodium saccharin.    -   1.41 Composition 1 or 1.1-1.61 wherein the composition comprises        a flavorant.    -   1.42 Composition 1 or 1.1-1.41 wherein the composition comprises        a visual aid.    -   1.43 Composition 1.42 wherein the visual aid is titanium        dioxide.    -   1.44 Composition 1 or 1.1-1.43 wherein the composition comprises        an anti-caries agent.    -   1.45 Composition 1.44 wherein the anti-caries agent is a        fluoride ion source.    -   1.46 Composition 1.45 wherein the fluoride ion source is        stannous fluoride, sodium fluoride, potassium fluoride, sodium        monofluorophosphate, sodium fluorosilicate, ammonium        fluorosilicate, amine fluoride (e.g.,        N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride),        ammonium fluoride, titanium fluoride, hexafluorosulfate, or a        mixture thereof.    -   1.47 Composition 1.46 wherein the anticaries agent is sodium        fluoride.    -   1.48 Composition 1 or 1.1-1.47 wherein the composition comprises        an anti-bacterial.    -   1.49 Composition 1.48 wherein the anti-bacterial agent is        triclosan, cetylpyridinium chloride (CPC), chlorhexidine (CHX),        stannous salts, essential oils, water soluble zinc salts, water        insoluble zinc salts, e.g., ZnO or zinc citrate, or a mixture        thereof, e.g., wherein the anti-bacterial agent is triclosan,        e.g., wherein the anti-bacterial agent is ZnO. e.g., wherein the        anti-bacterial agent is zinc citrate, e.g., wherein the        anti-bacterial agent is a mixture thereof.    -   1.50 Composition 1 or 1.1-1.49 wherein the composition comprises        an anti-attachment agent selected from Ethyl lauroyl arginate,        Delmopinol, chitosan, or a mixture thereof, e.g., wherein the        composition comprises Ethyl lauroyl arginate, e.g., wherein the        composition comprises Delmopinol, e.g., wherein the composition        comprises chitosan, e.g., wherein the composition comprises a        mixture thereof.    -   1.51 Composition 1 or 1.1-1.50 wherein the composition comprises        a whitening agent.    -   1.52 Composition 1.51 wherein the whitening agent is hydrogen        peroxide.    -   1.53 Composition 1.52 wherein the composition comprises a        polymer-peroxide complex, e.g., a cross-linked        poly(vinyl)pyrrolidone hydrogen peroxide complex.    -   1.54 Composition 1 or 1.1-1.53 wherein the composition comprises        a desensitizing agent, a vitamin, a preservative, an enzyme, or        a mixture thereof.    -   1.55 Composition 1 or 1.1-1.54 wherein the composition is a        mouthwash, toothpaste, tooth gel, tooth powder, non-abrasive        gel, mousse, foam, mouth spray, lozenge, oral tablet, dental        implement, or pet care product.    -   1.56 Composition 1 or 1.1-1.55 wherein the composition is a        mouthwash.    -   1.57 Composition 1 or 1.1-1.55 wherein the composition is a        toothpaste.    -   1.58 Any foregoing compositions wherein the phosphate/acrylate        co-polymer is a co-polymerized product of a mixture of acrylic        acid, methacrylic acid, and 2-hydroxyethyl methacrylate        phosphates of Formula 1:

-   -   -   wherein n is 0, 1 or 2.

    -   1.59 Any foregoing compositions wherein the phosphate/acrylate        co-polymer is a co-polymerized product of a mixture of acrylic        acid, methacrylic acid, and 2-hydroxyethyl methacrylate        phosphates of Formula 1 comprising acrylic acid in a molar        percentage of 80-90%, e.g., about 85%; methacrylic acid in a        molar percentage of 5-15%, e.g., about 11%, and hydroxyethyl        methacrylate phosphates of Formula 1 in a molar percentage of        2-6%, e.g., about 4%.

    -   1.60 Any foregoing compositions wherein the phosphate/acrylate        co-polymer has an average molecular weight of from 10 to 40 kDa,        e.g., 20 to 30 kDa.

    -   1.61 Any foregoing compositions wherein the phosphate/acrylate        copolymer is a random copolymer having a weight average        molecular weight of about 20,000 to 30,000 grams per mole that        is the copolymerized product of a mixture of acrylic acid,        methacrylic acid, and 2-hydroxyethy methacrylate phosphates of        Formula 1, e.g., in a molar ratio of about 85:11:4.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise water. Water employed in thepreparation of the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, should be deionized and free of organicimpurities. Water may make up the balance of the oral care composition.In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise 0 to 90 weight % water, e.g.,0.1 to 90 weight % water, e.g., 1 to 80 weight % water, e.g., 2 to 70weight % water, 5 to 60 weight % water, e.g., 5 to 50 weight % water,e.g., 20 to 60 weight % water, e.g., 10 to 40 weight % water. Thisamount of water includes the free water which is added plus that amountwhich is introduced with other components of the oral care composition,such as with sorbitol.

A thickener provides a desirable consistency and/or stabilizes and/orenhances performance (e.g., provides desirable active releasecharacteristics upon use) of the oral care composition. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise from 0.01 to 15 weight % of athickener, 0.1 to 15 weight % of a thickener, e.g., 0.1 to 10 weight %of a thickener, e.g., 0.1 to 5 weight % of a thickener, e.g., 0.5 to 10weight % of a thickener, e.g., 0.5 to 5 weight % of at a thickener,e.g., 1 to 4 weight % of a thickener, e.g., 2 to 5 weight %, of athickener, e.g., 2 to 4 weight % of a thickener, e.g., 3 to 4 weight %of a thickener. Higher weight percentages may be used for chewing gums,lozenges and breath mints, sachets, non-abrasive gels and subgingivalgels. Thickeners that may be used in the oral care compositionsdisclosed herein. e.g., Composition 1, e.g., 1.1-1.61, include, forexample, carboxyvinyl polymers, carrageenan (also known as carrageenangum), hydroxyethyl cellulose (HEC), natural and synthetic clays (e.g.,Veegum and laponite), water soluble salts of cellulose ethers (e.g.,sodium carboxymethylcellulose (CMC) and sodium carboxymethylhydroxyethyl cellulose), natural gums (e.g., gum karaya, xanthan gum,gum arabic, and gum tragacanth), colloidal magnesium aluminum silicate,silica (e.g., finely divided silica), polyvinyl pyrrolidone, carbowaxes,fatty acids and salts thereof, and mixtures thereof. In someembodiments, a mixture of thickening silica and carrageenan gum is usedas the thickener in the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61. In some embodiments, the oral carecompositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,comprise from 0.01 to 15 weight % of thickening silica and carrageenangum, 0.1 to 15 weight % of thickening silica and carrageenan gum, e.g.,0.1 to 10 weight % of thickening silica and carrageenan gum, e.g., 0.1to 5 weight % of thickening silica and carrageenan gum, e.g., 0.5 to 10weight % of thickening silica and carrageenan gum, e.g., 0.5 to 5 weight% of thickening silica and carrageenan gum, e.g., 1 to 4 weight % ofthickening silica and carrageenan gum, e.g., 2 to 5 weight % ofthickening silica and carrageenan gum, e.g., 2 to 4 weight % ofthickening silica and carrageenan gum, e.g., 3 to 4 weight % ofthickening silica and carrageenan gum.

A buffer adjusts the pH of oral care compositions, for example, to arange of about pH 4.0 to about pH 6.0. In some embodiments, the oralcare compositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,comprise from 0.1 to 10 weight % of a buffer, 0.5 to 10 weight % of abuffer, e.g., 0.5 to 5 weight % of a buffer, e.g., 0.5 to 4 weight % ofa buffer, e.g., 0.5 to 3 weight % of a buffer, e.g., 0.5 to 2 weight %of a buffer, e.g., 1 to 2 weight % of a buffer. Buffers that may be usedin the oral care compositions disclosed herein, e.g., Composition 1,e.g., 1.1-1.61, include, for example, sodium bicarbonate, sodiumphosphate {e.g., monosodium phosphate (NaH₂PO₄), disodium phosphate(Na₂HPO₄), trisodium phosphate (Na₃PO₄)}, sodium hydroxide, sodiumcarbonate, sodium acid pyrophosphate, citric acid, sodium citrate, andmixtures thereof. In some embodiments, sodium hydroxide is used as thebuffer in the oral care compositions disclosed herein, e.g., Composition1, e.g., 1.1-1.61. In some embodiments, the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61, comprise from 0.1to 10 weight % of sodium hydroxide, e.g., 0.5 to 10 weight % of sodiumhydroxide, e.g., 0.5 to 5 weight % of sodium hydroxide, e.g., 0.5 to 4weight % of sodium hydroxide, e.g., 0.5 to 3 weight % of sodiumhydroxide, e.g., 0.5 to 2 weight % of sodium hydroxide, e.g., 1 to 2weight % of sodium hydroxide.

A humectant keeps oral care compositions from hardening upon exposure toair. Certain humectants can also impart desirable sweetness or flavor tooral care compositions. In some embodiments, the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61, comprise, on apure humectant basis, from 0 to 70 weight % of a humectant, e.g., 10 to70 weight % of a humectant, e.g., 10 to 65 weight % of a humectant,e.g., 10 to 60 weight % of a humectant, e.g., 10 to 50 weight % of ahumectant, e.g., 20 to 50 weight % of at a humectant, e.g., 20 to 40weight % of a humectant. Humectants that may be used in the oral carecompositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,include, for example, glycerin, sorbitol, xylitol, butylene glycol,polyethylene glycol, propylene glycol, trimethyl glycine, and mixturesthereof. In some embodiments, a mixture of glycerin, sorbitol, andpropylene glycol is used as the humectant in the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise, on a pure humectant basis, from0 to 70 weight % of glycerin, sorbitol, and propylene glycol. e.g., 10to 70 weight % of glycerin, sorbitol, and propylene glycol, e.g., 10 to65 weight % of glycerin, sorbitol, and propylene glycol, e.g., 10 to 60weight % of glycerin, sorbitol, and propylene glycol, e.g., 10 to 50weight % of glycerin, sorbitol, and propylene glycol, e.g., 20 to 50weight % of glycerin, sorbitol, and propylene glycol, e.g., 20 to 40weight % of glycerin, sorbitol, and propylene glycol.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise a surfactant, e.g., selectedfrom anionic, cationic, zwitterionic, and nonionic surfactants, andmixtures thereof. In some embodiments, the surfactant is reasonablystable throughout a wide pH range. Surfactants are described in, forexample, U.S. Pat. No. 3,959,458, to Agricola et al; U.S. Pat. No.3,937,807, to Haefele; and U.S. Pat. No. 4,051,234, to Gieske et al. Insome embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise from 0.01 to 10 weight % of asurfactant. e.g., 0.05 to 5 weight % of a surfactant, e.g., 0.1 to 10weight % of a surfactant, e.g., 0.1 to 5 weight % of a surfactant, e.g.,0.1 to 2 weight % of a surfactant, e.g., 0.5 to 2 weight % of asurfactant. In some embodiments, the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, comprise from 0.01 to 10weight % of an anionic surfactant, e.g., 0.05 to 5 weight % of ananionic surfactant, e.g., 0.1 to 10 weight % of an anionic surfactant,e.g., 0.1 to 5 weight % of an anionic surfactant, e.g., 0.1 to 2 weight% of an anionic surfactant, e.g., 0.5 to 2 weight % of an anionicsurfactant, e.g., 1.5 weight % of an anionic surfactant.

Anionic surfactants that may be used in the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61, include, forexample,

-   -   i. water-soluble salts of higher fatty acid monoglyceride        monosulfates, such as the sodium salt of the monosulfated        monoglyceride of hydrogenated coconut oil fatty acids such as        sodium N-methyl N-cocoyl taurate, sodium cocomonoglyceride        sulfate,    -   ii. higher alkyl sulfates, such as sodium lauryl sulfate,    -   iii. higher alkyl-ether sulfates, e.g., of formula        CH₃(CH₂)_(m)CH₂(OCH₂CH₂)_(n)OSO₃X, wherein m is 6-16, e.g., 10,        n is 1-6, e.g., 2, 3 or 4, and X is Na or K, for example sodium        laureth-2 sulfate (CH₃(CH₂)₁₀CH₂(OCH₂CH₂)₂OSO₃Na),    -   iv. higher alkyl aryl sulfonates such as sodium dodecyl benzene        sulfonate (sodium lauryl benzene sulfonate), and    -   v. higher alkyl sulfoacetates, such as sodium lauryl        sulfoacetate (dodecyl sodium sulfoacetate), higher fatty acid        esters of 1,2 dihydroxy propane sulfonate, sulfocolaurate        (N-2-ethyl laurate potassium sulfoacetamide) and sodium lauryl        sarcosinate.

As used herein. “higher alkyl” refers to C₆₋₃₀ alkyl.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise an anionic surfactant. In someembodiments, the anionic surfactant is the water soluble salt of alkylsulfates having from 10 to 18 carbon atoms in the alkyl radical andwater soluble salts of sulfonated monoglycerides of fatty acids havingfrom 10 to 18 carbon atoms. Sodium lauryl sulfate, sodium lauroylsarcosinate, and sodium coconut monoglyceride sulfonates are examples ofanionic surfactants of that type. In some embodiments, the oral carecompositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,comprise sodium lauryl sulfate, sodium ether lauryl sulfate, or amixture thereof. In some embodiments, the oral care compositionsdisclosed herein. e.g., Composition 1, e.g., 1.1-1.61, comprise sodiumlauryl sulfate. In some embodiments, the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61, comprise from0.01 to 10 weight % sodium lauryl sulfate, e.g., 0.05 to 5 weight %sodium lauryl sulfate, e.g., 0.1 to 10 weight % sodium lauryl sulfate,e.g., 0.1 to 5 weight % o sodium lauryl sulfate, e.g., 0.1 to 2 weight %sodium lauryl sulfate, e.g., 0.5 to 2 weight % sodium lauryl sulfate,e.g., 1.5 weight % sodium lauryl sulfate.

An abrasive removes debris and surface stains. In some embodiments, theoral care compositions disclosed herein, e.g., Composition 1, e.g.,1.1-1.61, comprise 5 to 70 weight % of an abrasive, e.g., 5 to 60 weight% of an abrasive, e.g., 5 to 50 weight % of an abrasive, e.g., 5 to 40weight % of an abrasive, e.g., 5 to 30 weight % of an abrasive, e.g., 10to 30 weight % of an abrasive, e.g., 10 to 20 weight % of an abrasive.

Abrasives that may be used in the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, include, for example, acalcium phosphate abrasive, e.g., tricalcium phosphate (Ca₃(PO₄)₂),hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂), dicalcium phosphate dihydrate (CaHPO₄2H₂O, also sometimes referred to herein as DiCal), calciumpyrophosphate, and mixtures thereof. Calcium carbonate, e.g.,precipitated calcium carbonate, may also be employed as an abrasive.

Other abrasives that may be used in the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, include, for example,silica abrasives such as precipitated silicas having a mean particlesize of up to about 20 microns, such as Zeodent 115®, marketed by J. M.Huber, as well as sodium metaphosphate, potassium metaphosphate,aluminum silicate, calcined alumina, bentonite or other siliceousmaterials, or mixtures thereof. Silica abrasives used herein, as well asthe other abrasives, may have an average particle size ranging betweenabout 0.1 and about 30 microns, e.g., between about 5 and about 15microns. The silica abrasives may be from precipitated silica or silicagels, such as the silica xerogels described in U.S. Pat. No. 3,538,230to Pader et al. and U.S. Pat. No. 3,862,307 to Digiulio. Particularsilica xerogels are marketed under the trade name Syloid® by the W. R.Grace & Co. Davison Chemical Division. Precipitated silica materialsinclude those marketed by the J. M. Huber Corp. under the trade nameZeodent®, including the silica carrying the designation Zeodent 115 and119. Those silica abrasives are described in U.S. Pat. No. 4,340,583 toWason.

In some embodiments, abrasives that may be used in the oral carecompositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,include silica gels and precipitated amorphous silica having an oilabsorption value of about less than about 100 cc/100 g silica and in therange of about 45 cc/100 g to about 70 cc/100 g silica. Oil absorptionvalues are measured using the ASTA Rub-Out Method D281. In someembodiments, the silica comprises colloidal particles having an averageparticle size of about 3 microns to about 12 microns, and about 5 toabout 10 microns.

In some embodiments, the abrasive comprises a large fraction of verysmall particles, e.g., having a d50 less than about 5 microns, e.g.,small particle silica (SPS) having a d50 of about 3 to about 4 microns,e.g., Sorbosil AC43® (Ineos). Such small particles may be used informulations targeted at reducing hypersensitivity. The small particlecomponent may be present in combination with a second larger particleabrasive.

Low oil absorption silica abrasives that may be used in the oral carecompositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61, aremarketed under the trade designation Sylodent WXA® by Davison ChemicalDivision of W.R. Grace & Co., Baltimore, Md. 21203. Sylodent 650 XWA®, asilica hydrogel composed of particles of colloidal silica having a watercontent of about 29% by weight averaging about 7 to about 10 microns indiameter, and an oil absorption of less than about 70 cc/100 g of silicais an example of a low oil absorption silica abrasive that may be usedin the oral care compositions disclosed herein, e.g., Composition 1,e.g., 1.1-1.61.

In some embodiments, the oral care composition disclosed herein, e.g.,Composition 1, e.g, 1.1-1.61, comprise a high cleaning silica. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1. e.g., 1.1-1.61, comprise 5 to 70 weight % high cleaningsilica, e.g., 5 to 60 weight % high cleaning silica, e.g., 5 to 50weight % high cleaning silica, e.g., 5 to 40 weight % high cleaningsilica, e.g., 5 to 30 weight % high cleaning silica, e.g., 10 to 30weight % high cleaning silica, e.g., 10 to 20 weight % high cleaningsilica.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise a sweetener. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise 0.005 to 10 weight % of asweetener, e.g., 0.01 to 10 weight % of a sweetener, e.g., 0.1 to 10weight % of a sweetener, e.g., from 0.1 to 5 weight % of a sweetener,e.g., from 0.1 to 3 weight % of a sweetener, e.g., from 0.1 to 1 weight% of a sweetener, e.g., from 0.1 to 0.5 weight % of a sweetener.Sweeteners that may be used in the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, include, for example,sucrose, glucose, saccharin, sucralose, dextrose, levulose, lactose,mannitol, sorbitol, fructose, maltose, xylitol, saccharin salts (e.g.,sodium saccharin), thaumatin, aspartame, D-tryptophan, dihydrochalcones,acesulfame, cyclamate salts, and mixtures thereof. In some embodiments,sodium saccharin is used as the sweetener in the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise 0.005 to 10 weight % sodiumsaccharin, e.g., 0.01 to 10 weight % sodium saccharin, e.g., 0.1 to 10weight % sodium saccharin, e.g., from 0.1 to 5 weight % sodiumsaccharin, e.g., from 0.1 to 3 weight % sodium saccharin, e.g., from 0.1to 1 weight % sodium saccharin, e.g., from 0.1 to 0.5 weight % sodiumsaccharin.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise a flavorant. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise 0.1 to 5 weight % of aflavorant, e.g., 0.1 to 4 weight % of a flavorant, e.g., 0.1 to 3 weight% of a flavorant, e.g., 0.1 to 2 weight % of a flavorant, e.g., 0.5 to 2weight % of a flavorant, e.g., 0.6 to 2 weight % of a flavorant, e.g.,0.7 to 2 weight % of a flavorant, e.g., 0.8 to 2 weight % of a flavorante.g., 0.9 to 2 weight % of a flavorant, e.g., 1 to 2 weight % of aflavorant. Flavorants that may be used in the oral care compositionsdisclosed herein, e.g., Composition 1. e.g., 1.1-1.61, include, forexample, essential oils, as well as various flavoring aldehydes, esters,alcohols, and similar materials, as well as menthol, carvone, andanethole, as well as mixtures thereof. Examples of essential oilsinclude oils of spearmint, peppermint, wintergreen, sassafras, clove,sage, eucalyptus, marjoram, cinnamon, lemon, lime, grapefruit, andorange. In some embodiments, a mixture of peppermint oil and spearmintoil is used as the flavorant in the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise a visual aid, including but notlimited to a pigment, a dye, speckles, beads, strips, and mixturesthereof. In some embodiments, the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, comprise 0.001 to 20 weight% of a pigment, e.g., 0.01 to 20 weight % of a visual aid. e.g., 0.01 to20 weight % of a visual aid. e.g., 0.1 to 20 weight % of a visual aid,e.g., 0.1 to 10 weight % of a visual aid, e.g., 0.1 to 5 weight % of avisual aid, e.g., 0.1 to 3 weight % of a visual aid, e.g., 0.1 to 1weight % of a visual aid. In some embodiments, the oral carecompositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,comprise titanium dioxide. In some embodiments, the oral carecompositions disclosed herein, e.g., Composition 1. e.g., 1.1-1.61,comprise 0.001 to 20 weight % titanium dioxide, e.g., 0.01 to 20 weight% titanium dioxide, e.g., 0.01 to 20 weight % titanium dioxide, e.g.,0.1 to 20 weight % titanium dioxide. e.g., 0.1 to 10 weight % titaniumdioxide, e.g., 0.1 to 5 weight % titanium dioxide, e.g., 0.1 to 3 weight% titanium dioxide, e.g., 0.1 to 1 weight % titanium dioxide.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, further comprise an anti-caries agent. Insome embodiments, the oral care compositions disclosed herein, e.g.,Composition 1. e.g., 1.1-1.61, comprise 0.005 to 10 weight % of theanti-caries agent, e.g., 0.01 to 10 weight % of the anti-caries agent,e.g., 0.01 to 5 weight % of the anti-caries agent, e.g., 0.01 to 1weight % of the anti-caries agent, e.g., 0.01 to 0.3 weight % of theanti-caries agent, e.g., 0.1 to 10 weight % of the anti-caries agent,e.g., 0.1 to 5 weight % of the anti-caries agent, e.g., 0.1 to 2 weight% of the anti-caries agent, e.g., 0.1 to 1 weight % of the anti-cariesagent, e.g., 0.1 to 0.8 weight % of the anti-caries agent, e.g., 0.1 to0.6 weight % of the anti-caries agent, e.g., 0.1 to 0.5 weight % of theanti-caries agent. In some embodiments, the anti-caries agent is afluoride ion source. In some embodiments, the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61, further comprise0.005 to 10 weight % of the anti-caries agent which is a fluoride ionsource, e.g., 0.01 to 10 weight % of the anti-caries agent which is afluoride ion source, e.g., 0.01 to 5 weight % of the anti-caries agentwhich is a fluoride ion source, e.g., 0.01 to 1 weight % of theanti-caries agent which is a fluoride ion source, e.g., 0.01 to 0.3weight % of the anti-caries agent which is a fluoride ion source, e.g.,0.1 to 10 weight % of the anti-caries agent which is a fluoride ionsource, e.g., 0.1 to 5 weight % of the anti-caries agent which is afluoride ion source, e.g., 0.1 to 2 weight % of the anti-caries agentwhich is a fluoride ion source, e.g., 0.1 to 1 weight % of theanti-caries agent which is a fluoride ion source, e.g., 0.1 to 0.8weight % of the anti-caries agent which is a fluoride ion source, e.g.,0.1 to 0.6 weight % of the anti-caries agent which is a fluoride ionsource, e.g., 0.1 to 0.5 weight % of the anti-caries agent which is afluoride ion source. Examples of fluoride ion sources that may be usedin the oral compositions disclosed herein, e.g., Composition 1, e.g.,1.1-1.61, are found in U.S. Pat. No. 3,535,421 to Briner et al., U.S.Pat. No. 4,885,155 to Parran, Jr. et al., and U.S. Pat. No. 3,678,154 toWidder et al. Other examples of fluoride ion sources include, forexample, stannous fluoride, sodium fluoride, potassium fluoride, sodiummonofluorophosphate, sodium fluorosilicate, ammonium fluorosilicate,amine fluoride (e.g.,N′-octadecyltrimethylendiamine-N,N,N′-tris(2-ethanol)-dihydrofluoride),ammonium fluoride, titanium fluoride, hexafluorosulfate, andcombinations thereof. In certain embodiments the fluoride ion sourceincludes stannous fluoride, sodium fluoride, and sodiummonofluorophosphate, as well as mixtures thereof. In some embodiments,the anti-caries agent is sodium fluoride. In some embodiments, the oralcare compositions disclosed herein, e.g., Composition 1, e.g., 1.1-1.61,comprise 0.005 to 10 weight % sodium fluoride, e.g., 0.01 to 10 weight %sodium fluoride, e.g., 0.01 to 5 weight % sodium fluoride, e.g., 0.01 to1 weight % sodium fluoride, e.g., 0.01 to 0.3 weight % sodium fluoride,e.g., 0.1 to 10 weight % sodium fluoride, e.g., 0.1 to 5 weight % sodiumfluoride, e.g., 0.1 to 2 weight % sodium fluoride, e.g., 0.1 to 1 weight% sodium fluoride, e.g., 0.1 to 0.8 weight % sodium fluoride, e.g., 0.1to 0.6 weight % sodium fluoride, e.g., 0.1 to 0.5 weight % sodiumfluoride.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise the anti-caries agent which is afluoride ion source in an amount sufficient to supply 25 ppm to 25,000ppm of fluoride ions, e.g., from 100 to 20,000 ppm of fluoride ions,e.g., from 300 to 15,000 ppm of fluoride ions, e.g., from 500 to 10,000ppm of fluoride ions, e.g., from 500 to 8,000 ppm of fluoride ions,e.g., from 500 to 6,000 ppm of fluoride ions, e.g., from 500 to 4.000ppm of fluoride ions, e.g., from 500 to 2,000 ppm of fluoride ions,e.g., from 500 to 1,800 ppm of fluoride ions, e.g., from 1000 to 1600ppm, e.g., 1450 ppm of fluoride ions. The appropriate level of fluorideions will depend on the particular application. In some embodiments, atoothpaste for consumer use comprises the anti-caries agent which is afluoride ion source in an amount sufficient to supply from 1.000 to1,500 ppm of fluoride ions, with pediatric toothpaste having somewhatless. In some embodiments, a dentifrice or coating for professionalapplication comprises the anti-caries agent which is a fluoride ionsource in an amount sufficient to supply from 5,000 to 25,000 ppm offluoride ions.

In some embodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise an anti-bacterial oranti-attachment agent. In some embodiments, the oral care compositionsdisclosed herein, e.g., Composition 1, e.g., 1.1-1.61, comprise 0.01 to10 weight % of an anti-bacterial, e.g., 0.1 to 10 weight % of ananti-bacterial, e.g., 0.5 to 5 weight % of an anti-bacterial, e.g., 0.01to 5 weight % of an anti-bacterial. e.g., 0.05 to 4 weight % of ananti-bacterial, e.g., 0.05 to 3 weight % of an anti-bacterial, e.g.,0.05 to 2 weight % of an anti-bacterial, e.g., 0.05 to 1 weight % of ananti-bacterial, e.g., 0.1 to 1 weight % of an anti-bacterial, e.g., 0.1to 0.5 weight % of an anti-bacterial. The amount of the anti-bacterialwill vary depending on the type of oral care composition, with levelsused in toothpaste being, for example, 5 to 15 times greater than usedin mouthwash. For example, a mouthwash comprising triclosan maycomprise, e.g., 0.03 weight % triclosan while a toothpaste comprisingtriclosan toothpaste may comprise 0.3 weight % triclosan. Examples ofanti-bacterials that may be used in the oral compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, include, for example,halogenated diphenyl ether (e.g. triclosan), herbal extracts andessential oils (e.g., rosemary extract, tea extract, magnolia extract,thymol, menthol, eucalyptol, geraniol, carvacrol, citral, hinokitol,catechol, methyl salicylate, epigallocatechin gallate, epigallocatechin,gallic acid, miswak extract, sea-buckthorn extract), bisguanideantiseptics (e.g., chlorhexidine, alexidine or octenidine), quaternaryammonium compounds (e.g., cetylpyridinium chloride (CPC), benzalkoniumchloride, tetradecylpyridinium chloride (TPC).N-tetradecyl-4-ethylpyridinium chloride (TDEPC)), phenolic antiseptics,hexetidine, octenidine, sanguinarine, povidone iodine, delmopinol,salifluor, metal ions (e.g., zinc salts, for example, zinc citrate,stannous salts, copper salts, iron salts), sanguinarine, propolis andoxygenating agents (e.g., hydrogen peroxide, buffered sodiumperoxyborate or peroxycarbonate), phthalic acid and its salts,monoperthalic acid and its salts and esters, ascorbyl stearate, oleoylsarcosine, alkyl sulfate, dioctyl sulfosuccinate, salicylanilide,domiphen bromide, delmopinol, octapinol and other piperidinoderivatives, nicin preparations, chlorite salts, methyl hydroxybenzoate,and mixtures thereof. In some embodiments, the anti-bacterial istriclosan. In some embodiments, the oral care compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, comprise 0.01 to 10 weight% triclosan, e.g., 0.1 to 10 weight % triclosan, e.g., 0.5 to 5 weight %triclosan, e.g., 0.01 to 5 weight % triclosan, e.g., 0.05 to 4 weight %triclosan, e.g., 0.05 to 3 weight % triclosan. e.g., 0.05 to 2 weight %triclosan. e.g., 0.05 to 1 weight % triclosan. e.g., 0.1 to 1 weight %triclosan, e.g., 0.1 to 0.5 weight % triclosan.

A whitening agent whitens a tooth to which it is applied. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise a whitening agent. In someembodiments, the oral care compositions disclosed herein, e.g.,Composition 1, e.g., 1.1-1.61, comprise a whitening agent in a dentalsurface-whitening effective amount, e.g., 0.1 to 90 weight % whiteningagent, e.g., 0.5 to 50 weight % whitening agent, e.g., 1 to 30 weight %whitening agent, e.g., 2 to 10 weight % whitening agent. Examples ofwhitening agents that may be used in the oral compositions disclosedherein, e.g., Composition 1, e.g., 1.1-1.61, include, for example,peroxides, metal chlorites, perborates, percarbonates, peroxyacids,hypochlorites, and mixtures thereof. In some embodiments, the whiteningagent is hydrogen peroxide or a hydrogen peroxide source, for example,urea peroxide or a peroxide salt or complex (for example,peroxyphosphate, peroxycarbonate, perborate, peroxysilicate, orpersulphate salts; for example calcium peroxyphosphate, sodiumperborate, sodium carbonate peroxide, sodium peroxyphosphate, andpotassium persulfate), or a hydrogen peroxide polymer complex (forexample, a peroxide-polyvinyl pyrrolidone polymer complex).

In some embodiments, an oral care composition disclosed hereincomprises:

Ingredient % 70% Sorbitol 20 99.0%-101.0% Glycerin 20 Water Q.S. HighCleaning Silica 10 Gantrez S-97 (B.F.) - Liquid (13% assay) 15 AbrasiveSilica 8.8 Thickening Silica 2.7 Phosphate/acrylate polymer (as a.i.)0.4-2.4 Sodium Lauryl Sulfate 1.5 Sodium Hydroxide   0-1.2 Sodium CMC -Type 12 1.1 Flavor 1.0-1.2 Titanium Dioxide 0.75 Propylene Glycol 0.5Carrageenan Gum 0.48 Triclosan USP 0.3 Sodium Saccharin 0.3

In some embodiments, an oral care composition disclosed hereincomprises:

Ingredient % 70% Sorbitol 14 99.0%-101.0% Glycerin 17 Water Q.S. HighCleaning Silica 17 Gantrez S-97 (B.F.) - Liquid (13% assay) 17Thickening Silica 2.7 Phosphate/acrylate polymer (as a.i.) 0.4-2.4Sodium Lauryl Sulfate 1.5 Sodium Hydroxide   0-1.2 Sodium CMC - Type 121.1 Xanthan Gum 0.8 Flavor 1.0-1.2 Titanium Dioxide 0.5 Propylene Glycol0.5 Carrageenan Gum 0.48 Triclosan USP 0.3 Sodium Saccharin 0.3 SodiumFluoride 0.243

In some embodiments, an oral care composition disclosed hereincomprises:

Ingredient % 70% Sorbitol 20 99.0%-101.0% Glycerin 20 Water Q.S. HighCleaning Silica 10 Abrasive Silica 8.8 Thickening Silica 2.7Phosphate/acrylate polymer (as a.i.) 0.4-2.4 Gantrez (as a.i.) 0-2Tetrasodium Pyrophosphate (sodium pyrophosphate) 0-2 SodiumTripolyphosphate 0-3 Sodium Lauryl Sulfate 1.5 Sodium Hydroxide   0-1.2Sodium CMC - Type 12 1.1 Flavor 1.0-1.2 Titanium Dioxide 0.75 PropyleneGlycol 0.5 Carrageenan Gum 0.48 Sodium Saccharin 0.3 Sodium Fluoride0.243

Any of the preceding oral care compositions, wherein the composition isa mouthwash, toothpaste, tooth gel, tooth powder, non-abrasive gel,mousse, foam, mouth spray, lozenge, oral tablet, dental implement, orpet care product.

Any of the preceding oral care compositions, wherein the composition isa mouthwash.

Any of the preceding oral care compositions, wherein the composition isa toothpaste.

Further provided is a method (Method A) for the treatment and/orinhibition of a chemical stain, plaque, and/or tartar on a dentalsurface, comprising contacting the dental surface with any of thepreceding oral care compositions.

Further provided herein is Method A as follows:

-   -   A.1 Method A wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   A.2 Method A or A.1 wherein the method is for the treatment of a        chemical stain, plaque, acid erosion, and/or tartar on the        dental surface.    -   A.3 Method A.2 wherein the method is for the treatment of a        chemical stain on the dental surface.    -   A.4 Method A.2 wherein the method is for the treatment of plaque        on the dental surface.    -   A.5 Method A.2 wherein the method is for the treatment of acid        erosion on the dental surface.    -   A.6 Method A.2 wherein the method is for the treatment of tartar        on the dental surface.    -   A.7 Method A or A.1 wherein the method is for the inhibition of        a chemical stain, plaque, and/or tartar on the dental surface.    -   A.8 Method A.7 wherein the method is for the inhibition of a        chemical stain on the dental surface.    -   A.9 Method A.7 wherein the method is for the inhibition of        plaque on the dental surface.    -   A.10 Method A.7 wherein the method is for the inhibition of acid        erosion on the dental surface.    -   A.11 Method A.7 wherein the method is for the inhibition of        tartar on the dental surface.    -   A.12 Method A or A.1-A.11 wherein the dental surface is a human        tooth.    -   A.13 Method A or A.1-A.12 wherein the composition is contacted        with the dental surface by brushing.

Further provided is a method (Method B) for the treatment and/orinhibition of gum disease comprising contacting the oral cavity with anyof the preceding oral care compositions.

Further provided herein is Method B as follows:

-   -   B.1 Method B wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   B.2 Method B or B.1 wherein the method is for the treatment of        gum disease.    -   B.3 Method B, B.1, or B.2 wherein the gum disease is gingivitis.    -   B.4 Method B, B.1, or B wherein the gum disease is        periodontitis.    -   B.5 Method B or B.1 wherein the method is for the inhibition of        gum disease.    -   B.6 Method B, B.1, or B.5 wherein the gum disease is gingivitis.    -   B.7 Method B, B.1, or B.5 wherein the gum disease is        periodontitis.    -   B.8 Method B or B.1-B.7 wherein the oral cavity is a human oral        cavity.    -   B.9 Method B or B.1-B.8 wherein the composition is contacted        with the oral cavity by brushing.

Further provided is a method (Method C) for the treatment and/orinhibition of halitosis comprising contacting the oral cavity with anyof the preceding oral care compositions.

Further provided herein is Method C as follows:

-   -   C.1 Method C wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   C.2 Method C or C.1 wherein the oral cavity is a human oral        cavity.    -   C.3 Method C, C.1, or C.2 wherein the composition is contacted        with the oral cavity by brushing.

Further provided is a method (Method D) for inhibiting biofilm formationon a dental surface comprising contacting the dental surface with any ofthe preceding oral care compositions.

Further provided herein is Method D as follows:

-   -   D.1 Method D wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   D.2 Method D or D.1 wherein the dental surface is a human tooth.    -   D.3 Method D, D.1, or D.2 wherein the composition is contacted        with the dental surface by brushing.

Further provided is a method (Method E) for treating and/or inhibitingbacteria from sticking together and growing into bigger colonies in anoral cavity comprising contacting the oral cavity with any of thepreceding oral care compositions.

Further provided herein is Method E as follows:

-   -   E.1 Method E wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   E.2 Method E or E.1 wherein the oral cavity is a human oral        cavity.    -   E.3 Method E, E.1, or E.2 wherein the composition is contacted        with the oral cavity by brushing.

Further provided is a use (Use A) of any of the preceding oral carecompositions for the treatment and/or inhibition of a chemical stain,plaque, and/or tartar on a dental surface.

Further provided herein is Use A as follows:

-   -   A.1 Use A wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   A.2 Use A or A.1 wherein the use is for the treatment of a        chemical stain, plaque, acid erosion, and/or tartar on the        dental surface.    -   A.3 Use A.2 wherein the use is for the treatment of a chemical        stain on the dental surface.    -   A.4 Use A.2 wherein the use is for the treatment of plaque on        the dental surface.    -   A.5 Use A2 wherein the use is for the treatment of acid erosion        on the dental surface.    -   A.6 Use A.2 wherein the use is for the treatment of tartar on        the dental surface.    -   A.7 Use A or A.1 wherein the use is for the inhibition of a        chemical stain, plaque, acid erosion, and/or tartar on the        dental surface.    -   A.8 Use A.7 wherein the use is for the inhibition of a chemical        stain on the dental surface.    -   A.9 Use A.7 wherein the use is for the inhibition of plaque on        the dental surface.    -   A.10 Use A.7 wherein the use is for the inhibition of acid        erosion on the dental surface.    -   A.11 Use A.7 wherein the use is for the inhibition of tartar on        the dental surface.    -   A.12 Use A or A.1-A.11 wherein the dental surface is a human        tooth.    -   A.13 Use A or A.1-A.12 wherein the composition is contacted with        the dental surface by brushing.

Further provided is a use (Use B) of any of the preceding oral carecompositions for the treatment and/or inhibition of gum disease in anoral cavity.

Further provided herein is Use B as follows:

-   -   B.1 Use B wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   B.2 Use B or B.1 wherein the use is for the treatment of gum        disease.    -   B.3 Use B, B.1, or B.2 wherein the gum disease is gingivitis.    -   B.4 Use B, B.1, or B wherein the gum disease is periodontitis.    -   B.5 Use B or B.1 wherein the use is for the inhibition of gum        disease.    -   B.6 Use B, B.1, or B.5 wherein the gum disease is gingivitis.    -   B.7 Use B, B.1, or B.5 wherein the gum disease is periodontitis.    -   B.8 Use B or B.1-B.7 wherein the oral cavity is a human oral        cavity.    -   B.9 Use B or B.1-B.8 wherein the composition is contacted with        the oral cavity by brushing.

Further provided is a use (Use C) of any of the preceding oral carecompositions for the treatment and/or inhibition of halitosis in an oralcavity.

Further provided herein is Use C as follows:

-   -   C.1 Use C wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   C.2 Use C or C.1 wherein the oral cavity is a human oral cavity.    -   C.3 Use C, C.1, or C.2 wherein the composition is contacted with        the oral cavity by brushing.

Further provided is a use (Use D) of any of the preceding oral carecompositions for the inhibition of biofilm formation on a dentalsurface.

Further provided herein is Use D as follows:

-   -   D.1 Use D wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   D.2 Use D or D.1 wherein the oral cavity is a human oral cavity.    -   D.3 Use D, D.1, or D.2 wherein the composition is contacted with        the oral cavity by brushing.

Further provided is a use (Use E) of any of the preceding oral carecompositions for treating and/or inhibiting bacteria from stickingtogether and growing into bigger colonies in an oral cavity.

Further provided herein is Use E as follows:

-   -   E.1 Use E wherein the composition is Composition 1, e.g.,        1.1-1.61.    -   E.2 Use E or E.1 wherein the oral cavity is a human oral cavity.    -   E.3 Use E, E.1, or E.2 wherein the composition is contacted with        the oral cavity by brushing.

As used herein, “inhibition” refers to reduction of stains that wouldotherwise form or develop subsequent to the time of the treatment. Suchinhibition can range from a small but observable or measurable reductionto complete inhibition of subsequent staining, by comparison with anuntreated or placebo-treated dental surface.

Where the dental surface is substantially free of chemical stains,Method A, e.g., A.1-A.10, and Use B, e.g., B.1-B.10, are effective toinhibit formation and development of new chemical stains, as can occurfor example by oral use of tobacco products (including smoking) or bydrinking tea, coffee, red wine, or coke, subsequent to treatmentaccording to the method. Where the dental surface already possesses somedegree of chemical staining, Method A, e.g., A.1-A.10, and Use B, e.g.,B.1-B.10, are effective to inhibit further development of the existingstain. In some embodiments, the Method A, e.g., A.1-A.10, and Use B,e.g., B.1-B.10, can remove, partially or completely, an existingchemical stain as well as inhibit subsequent staining.

Also provided is a method of forming any of the compositions 1.1-1.61 asa mouth rinse that includes the phosphate/acrylate co-polymer and thesynthetic anionic linear polycarboxylate polymer as well as a zinc saltand a cationic antibacterial agent. The method can form a stablecomposition that is stable and transparent. The method comprises thefollowing steps:

-   (I) mixing water, surfactant, and a cationic antibacterial agent    (such as CPC) in a mixing tank to form a main mix;-   (II) mixing 10-20 weight % of the total water, optionally 14-16 or    15 weight % of the total water, the phosphate/acrylate co-polymer,    and polyols (such as glycerin and/or sorbitol) to form a first    premix,-   (III) mixing 10-20 weight % of the total water, optionally 14-16 or    15 weight % of the total water first with the zinc salt (such as    water soluble zinc salt, such as zinc chloride) and then adding the    synthetic anionic linear polycarboxylate polymer (Gantrez) to form a    second premix,-   (IV) mixing the first premix into the main mix,-   (V) after the first premix is added, mixing the second premix into    the main mix,-   (VI) optionally, mixing flavor and/or cooling agents with a glycol    to form a third premix and adding the third premix to the main mix    after the second premix is added.

Any additional materials, such as sweeteners, fluoride, colorants, andpreservatives can be added to the main mix prior to the premixes beingadded.

EXAMPLES Example 1 Stain Prevention Efficacy

Sample composition with phosphate/acrylate polymer are shown in Table 2.

TABLE 2 Ingredient % 70% Sorbitol 20 99.0%-101.0% Glycerin 20 Water Q.S.High Cleaning Silica 10 Abrasive Silica 8.8 Thickening Silica 2.7Phosphate/acrylate polymer (as a.i.) 0.4-2.4 Gantrez (as a.i.) 0-2Tetrasodium Pyrophosphate (sodium pyrophosphate) 0-2 SodiumTripolyphosphate 0-3 Sodium Lauryl Sulfate 1.5 Sodium Hydroxide   0-1.2Sodium CMC - Type 12 1.1 Flavor   1-1.2 Titanium Dioxide 0.75 PropyleneGlycol 0.5 Carrageenan Gum 0.48 Sodium Saccharin 0.3 Sodium Fluoride0.243

In vitro stain inhibition testing is conducted on hydroxyapatite discs(HAP discs). The efficacy is quantified by measuring the light reflectedfrom the surface of the HAP disc after treatment of the HAP disc with a1:2 dentifrice/water slurry and subsequent exposure to a staining agent,in this case, coffee. The measurement is taken with a chromameter andL*a*b* value recorded. The HAP disc is first soaked in saliva overnightand baseline whiteness is measured, next it is treated with 1:2dentifrice/water slurry for 5 minutes and the initial L*a*b* isrecorded. The HAP disc is then exposed to a coffee for 15 minutes,rinsed with distilled ionized water and incubated in saliva for 20minutes. The above staining process is repeated for a total of threetimes and the final L*a*b* is read. This value is compared to theinitial L*a*b* to quantify the dentifrice inhibition of the coffee stainformation on the HAP disc. The lower the delta L*, the better staininhibition effect provided by the dentifrice. The results are displayedin Table 3.

TABLE 3 In vitro stain inhibition Composition Delta L Control 1 37Control 2 30 0.4% polymer 34 1.4% polymer 30 2.4% polymer 25 0.4%polymer + 2% Gantrez 23

All dentifrices with the phosphate/acrylate polymer show improvedanti-stain efficacy than Control Toothpaste 1, some are comparable to oreven better than the positive control of commercialized silica-baseControl Toothpaste 2 which contains phosphate salts. The results alsoshow a dose response of phosphate/acrylate polymer with anti-stainefficacy and 2.4% phosphate/acrylate polymer (as a.i.) shows the mostanti-stain efficacy. The dentifrice with a combination ofphosphate/acrylate polymer and Gantrez delivers similar anti-stainefficacy as the 2.4% phosphate/acrylate polymer alone.

Phosphate salts are also formulated together with thisphosphate/acrylate polymer into dentifrice to further enhance efficacy.The test results are shown in Table 4. The results show phosphate saltsfurther enhance the anti-stain efficacy compared to formulae withphosphate/acrylate polymer only and achieve comparable efficacy to both2.4% phosphate/acrylate polymer (as a.i.) and 0.4% phosphate/acrylatepolymer (as a.i.) plus 2% Gantrez.

TABLE 4 Stain Prevention in Dentifrice Composition Delta L Control 29.50.4% polymer 33.5 0.4% polymer TSPP/STPP 26 1.4% polymer 29.5 1.4%polymer TSPP/STPP 22.6 2.4% polymer 24.8 0.4% polymer + 2% Gantrez 22.6

Example 2 Stable Mouthwash with Incompatible Materials

A stable mouthwash as evidenced by low turbidity that containsincompatible ingredients can be prepared. A cationic material can beincluded with the phosphate/acrylate polymer by inclusion of syntheticanionic linear polycarboxylate polymer. The cationic material iscetylpyridinium chloride. Test mouthwashes are prepared as below inTable 5. Each contain 0.1 weight % CPC and 0.08 weight % zinc chloride.

TABLE 5 Formulation Materials (weight %) A 0.1% CPC, 0.08% zincchloride, 0% Gantrez, 0.3125-2.5% phosphate/acrylate polymer (specificexample 1.25%) B 0.1% CPC, 0.08% zinc chloride, 1% Gantrez, 0.3125-1%phosphate/acrylate polymer (specific example 0.625%) C 0.1% CPC, 0.08%zinc chloride, 1% Gantrez, 1.25-2% phosphate/acrylate polymer (specificexample 1.25%)

The formulas above are prepared by creating three premixes to add to amain mixing tank. In a main mixing tank, water, surfactants, sweeteners,fluoride, CPC, potassium sorbate, and dye are added and mixed. A firstpremix is prepared with the phosphate/acrylate polymer, 15% of the totalwater, and polyols (glycerin and sorbitol). This premix is added to themain mix tank. A second premix is prepared with zinc chloride, 15% ofthe total water, and the Gantrez. This premix is added to the main mixtank. A third premix is prepared with propylene glycol, cooling agentsand/or flavoring agents. This premix is then added to the main mixingtank.

Turbidity for commercial products is typically 0-13 NTU. Turbidity ismeasured using a Hach turbidity meter at 25° C. after 24 hours of makingthe composition. Turbidity is the cloudiness or haziness of a fluidcaused by individual particles (suspended solids) that are generally notperceptible to the naked eye.

Formulations under A were all turbid. Formulations under B were allTurbid. Formulations under C had acceptable turbidity, which means thatthe materials are stable together and do not precipitate out. Table 6below has the turbidity measurements for the representative samples forA, B, and C.

TABLE 6 Formulation Materials (weight %) NTU A 0.1% CPC, 0.08% zincchloride, 0% Gantrez, 168 1.25% phosphate/acrylate polymer B 0.1% CPC,0.08% zinc chloride, 1% Gantrez, 179 0.625% phosphate/acrylate polymer C0.1% CPC, 0.08% zinc chloride, 1% Gantrez, 8.9 1.25% phosphate/acrylatepolymer

As can be seen in Table 6, formulations A without the combination of thephosphate/acrylate polymer and the synthetic anionic linearpolycarboxylate polymer were turbid. Formulations B with a low level ofphosphate/acrylate polymer were also turbid. Formulations C with asufficient amount of phosphate/acrylate polymer with the syntheticanionic linear polycarboxylate polymer were able to stabilize thespecific amount of CPC and zinc chloride.

What is claimed is:
 1. An oral care composition comprising aphosphate/acrylate co-polymer, a synthetic anionic linearpolycarboxylate polymer, and an orally acceptable carrier, and whereinthe phosphate/acrylate co-polymer is a co-polymerized product of amixture of acrylic acid, methacrylic acid, and a mixture of2-hydroxyethyl methacrylate phosphates of Formula 1:

wherein n is 0, 1 or
 2. 2. The composition of claim 1, wherein thecomposition comprises 0.1 to 10 weight % phosphate/acrylate co-polymer.3. The composition of claim 1, wherein the composition comprises 0.01 to30 weight % synthetic anionic linear polycarboxylate.
 4. The compositionof claim 1, wherein the synthetic anionic linear polycarboxylate is acopolymer of maleic anhydride or acid and methyl vinyl ether.
 5. Thecomposition of claim 1, wherein the synthetic anionic linearpolycarboxylate is 1:4 to 4:1 copolymer of methyl vinyl ether and maleicanhydride, wherein the anhydride is hydrolyzed after co-polymerizationto provide the acid, having a weight average molecular weight (M.W.) ofabout 30,000 to about 1,000,000 Da.
 6. The composition of claim 1 whichis a toothpaste comprising a silica abrasive.
 7. The composition ofclaim 1, wherein the composition comprises an anti-bacterially effectiveamount of an antibacterial agent selected from the group consisting oftriclosan, cetylpyridinium chloride (CPC), chlorhexidine (CHX), stannoussalts, water soluble zinc salts, water insoluble zinc compounds, zincoxide, zinc citrate, or a mixture thereof, optionally the antibacterialagent is triclosan.
 8. The composition of claim 1, wherein thephosphate/acrylate co-polymer is a co-polymerized product of a mixtureof acrylic acid, methacrylic acid, and 2-hydroxyethyl methacrylatephosphates of Formula 1 comprising acrylic acid in a molar percentage of70-90%; methacrylic acid in a molar percentage of 5-20%, andhydroxyethyl methacrylate phosphates of Formula 1 in a molar percentageof 1-10%.
 9. The composition of claim 1, wherein the phosphate/acrylateco-polymer is a co-polymerized product of a mixture of acrylic acid,methacrylic acid, and 2-hydroxyethyl methacrylate phosphates of Formula1 comprising acrylic acid in a molar percentage of 80-90% or 85%;methacrylic acid in a molar percentage of 5-15% or 11%, and hydroxyethylmethacrylate phosphates of Formula 1 in a molar percentage of 2-6% or4%.
 10. The composition of claim
 1. wherein the phosphate/acrylatecopolymer is a random copolymer having a weight average molecular weightof 10,000 to 500,000 Da, and the phosphate/acrylate copolymer is belowits glass transition temperature.
 11. The composition of claim 10,wherein the weight average molecular weight is 10,000 to 200,000 Da,optionally, 10,000 to 40,000, 15,000 to 25,000, or 17,000 to 23,000 Da.12. The composition of claim 1 which is a toothpaste or a mouthwash. 13.A method for the treatment and/or inhibition of a chemical stain,plaque, acid erosion, and/or tartar on a dental surface, comprisingcontacting the dental surface with a composition of claim
 1. 14. Amethod for the treatment and/or inhibition of gum disease comprisingcontacting the oral cavity with a composition of claim
 1. 15. A methodfor the treatment and/or inhibition of halitosis comprising contactingthe oral cavity with a composition of claim
 1. 16. A method for theinhibition of biofilm formation on a dental surface comprisingcontacting the oral cavity with a composition of claim
 1. 17. A methodfor treating and/or inhibiting bacteria from sticking together andgrowing into bigger colonies in an oral cavity comprising contacting theoral cavity with a composition of claim
 1. 18. A method of forming thecomposition of claim 1 as a mouth rinse that includes a zinc salt and acationic antibacterial agent comprising: (I) mixing water, surfactant,and a cationic antibacterial agent in a mixing tank to form a main mix;(II) mixing 10-20 weight % of the total water, optionally 14-16 or 15weight % of the total water, the phosphate/acrylate co-polymer, and apolyol to form a first premix, (III) mixing 10-20 weight % of the totalwater, optionally 14-16 or 15 weight % of the total water first with thezinc and then adding the synthetic anionic linear polycarboxylatepolymer (Gantrez) to form a second premix, (IV) mixing the first premixinto the main mix, (V) after the first premix is added, mixing thesecond premix into the main mix, (VI) optionally, mixing flavor and/orcooling agents with a glycol to form a third premix and adding the thirdpremix to the main mix after the second premix is added.
 19. The methodof claim 18, wherein the cationic antibacterial active iscetylpyridinium chloride and the zinc salt is zinc chloride.